WO2014196459A1 - カーボンナノチューブシートおよびカーボンナノチューブシートの製造方法 - Google Patents

カーボンナノチューブシートおよびカーボンナノチューブシートの製造方法 Download PDF

Info

Publication number
WO2014196459A1
WO2014196459A1 PCT/JP2014/064358 JP2014064358W WO2014196459A1 WO 2014196459 A1 WO2014196459 A1 WO 2014196459A1 JP 2014064358 W JP2014064358 W JP 2014064358W WO 2014196459 A1 WO2014196459 A1 WO 2014196459A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon nanotube
sheet
layer
composite
group
Prior art date
Application number
PCT/JP2014/064358
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
井上　鉄也
怜史 今坂
Original Assignee
日立造船株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日立造船株式会社 filed Critical 日立造船株式会社
Priority to EP14808111.0A priority Critical patent/EP3006398A4/de
Priority to KR1020157030747A priority patent/KR102293908B1/ko
Priority to US14/895,061 priority patent/US9902618B2/en
Priority to CN201480022076.2A priority patent/CN105164049B/zh
Publication of WO2014196459A1 publication Critical patent/WO2014196459A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes

Definitions

  • the present invention relates to a carbon nanotube sheet and a method for producing the carbon nanotube sheet.
  • Carbon nanotubes are materials with various characteristics and are expected to be applied in many fields.
  • a vertically aligned carbon nanotube group obtained by vertically aligning individual carbon nanotubes that is, a group of vertically aligned carbon nanotubes, has a large surface area, and thus the characteristics of the carbon nanotube are extracted, and the application range is wide.
  • Such a group of vertically aligned carbon nanotubes is generally formed on the surface of a substrate during the manufacturing process.
  • a method for peeling the vertically aligned carbon nanotube group from the surface of the substrate a method using water and its temperature has been proposed (see, for example, Patent Document 1).
  • the carbon nanotube group can be peeled from the substrate while maintaining the shape characteristics formed on the substrate.
  • an object of the present invention is to provide a carbon nanotube sheet that can maintain the sheet shape even in a large area and can improve the characteristics of the carbon nanotube, and a method for producing the carbon nanotube sheet.
  • a carbon nanotube sheet according to claim 1 of the present invention includes a carbon nanotube layer formed by vertically aligning countless carbon nanotubes, and a fibrous carbonized layer that holds the base end portion of the carbon nanotubes And
  • the carbon nanotube layer is a state in which the front end portion and the base end portion of the carbon nanotube fall and the intermediate portion is intertwined.
  • a method of manufacturing a carbon nanotube sheet according to claim 2 of the present invention includes a composite step of forming a composite sheet by heating a thermocarbonized sheet and pressing it against a group of carbon nanotubes. , By heating the composite sheet in an inert gas atmosphere, and carbonizing the thermal carbonizable sheet in the composite sheet, When the said heat carbonizable sheet
  • the composite sheet in the carbonization step of the production method according to claim 2 is restricted by a stiffening member.
  • the carbon nanotube groups in the composite process of the production method according to claim 2 or 3 are obtained by combining two vertically aligned carbon nanotube groups with each other. It is laminated by pressing.
  • the carbon nanotube sheet manufacturing method according to claim 5 of the present invention is the manufacturing method according to claim 4, wherein the two vertically aligned carbon nanotube groups are each composed of the length of the carbon nanotube constituting each of And / or different densities.
  • the manufacturing method of the carbon nanotube sheet which concerns on Claim 7 of this invention is a carbonization process from the place where the thermal carbonization sheet of the manufacturing method as described in any one of Claim 2 thru
  • the sheet shape can be maintained even when the area is large, and the characteristics of the carbon nanotube can be improved.
  • Example 1 of the present invention It is an expanded sectional view of the carbon nanotube sheet concerning Example 1 of the present invention, (a) is a carbon nanotube layer having a brush shape, and (b) is a carbon nanotube layer having an entanglement shape. It is an enlarged photograph by SEM of the carbon nanotube sheet, (a) shows a 500 times cross section, (b) shows a 2000 times cross section, and (c) shows a 5000 times cross section. It is an enlarged photograph by SEM of a entangled carbon nanotube layer, (a) shows a surface of 11000 times, (b) shows a surface of 10,000 times, and (c) shows a cross section of 13000 times. It is a schematic process drawing which shows the manufacturing method of the carbon nanotube sheet.
  • this carbon nanotube sheet 1 includes a carbon nanotube layer 3 formed by vertically aligning countless carbon nanotubes, and the base ends of individual carbon nanotubes in order to maintain the layer shape of the carbon nanotube layer 3. And a fibrous carbonized layer 4 holding the part. That is, since the base end portion of the carbon nanotube is held by the fibrous carbonized layer 4, the carbon nanotube layer 3 does not vary even if it has a brush shape as shown in FIG. . Of course, if the carbon nanotube layer 3 has the entangled shape shown in FIG. 1B, the carbon nanotubes are bonded to each other by van der Waals force, and therefore, the carbon nanotube layer 3 is more difficult to be separated.
  • the entangled shape means a state in which the distal end portion and the proximal end portion of the carbon nanotube are tilted and the intermediate portion is entangled.
  • FIGS. 2 and 3 Magnified photographs by SEM of the carbon nanotube sheet 1 and the entangled carbon nanotube layer 3 are shown in FIGS. 2 and 3, respectively.
  • 2 indicates the fibers of the carbonized layer 4
  • FIGS. 2B and 2C are enlarged photographs of the range of b and c in FIG. 2A.
  • FIGS. 2 (a) to 2 (c) it can be seen that the fibers 4f of the carbonized layer 4 are welded and entangled with the carbon nanotube layer 3.
  • 3 (a) and 3 (b) show the surface of the entangled carbon nanotube layer 3
  • FIG. 3 (c) shows a cross section of the entangled carbon nanotube layer 3.
  • reference numeral 3t indicates a tip portion of the carbon nanotube (tilted obliquely)
  • reference numeral 3m indicates an intermediate portion of the carbon nanotube (entangled substantially in the vertical direction)
  • reference numeral 3r indicates the carbon nanotube.
  • the base end part is shown.
  • the entangled carbon nanotube layer 3 shown in FIG. 3 has a thickness of about 180 ⁇ m that is about 8 to 10 ⁇ m by pressing.
  • the carbon nanotube layer 3 is not separated by the fibrous carbonized layer 4, even if the carbon nanotube sheet 1 has a large area that is recovered by a roll, the sheet shape does not collapse.
  • the carbon nanotube layer 3 can be obtained in a sheet shape.
  • the carbon nanotube layer 3 when the carbon nanotube layer 3 is entangled, the wettability and thermal conductivity of the obtained carbon nanotube sheet 1 can be improved, and the maintenance of the sheet shape can be further strengthened.
  • a method for producing the carbon nanotube sheet 1 will be described.
  • the carbon nanotube layer 3 having a brush shape will be described as an example.
  • This manufacturing method will be schematically described.
  • a composite sheet is obtained by combining a carbon nanotube group and a film sheet made of a thermosetting resin (resin such as phenol, epoxy, melanin, urea, alkyd).
  • a carbonizing step 74 that carbonizes the film sheet of the composite sheet to form a fibrous carbonized layer 4.
  • the film sheet made of the thermosetting resin is an example of a thermocarbonized sheet.
  • the thermal carbonizable sheet may be a film sheet that is carbonized and becomes fibrous when heated.
  • the film sheet made of a thermosetting resin a cellulose-based nonwoven fabric sheet derived from wood is used.
  • the film sheet made of the thermosetting resin is simply referred to as a film sheet.
  • the carbon nanotube group has the same configuration as the carbon nanotube layer 3 and is formed by collecting countless carbon nanotubes in a brush shape. However, since the carbon nanotube group is a single body before being held by the carbonized layer 4, the carbon nanotube layer 3 Are called as such.
  • the composite sheet composed of the carbon nanotube group and the film sheet is formed by heating the film sheet and pressing it against the carbon nanotube group.
  • the composite sheet is heated in a nitrogen gas atmosphere, whereby the film sheet is carbonized to become the fibrous carbonized layer 4. Since the carbonized layer 4 and the carbon nanotube layer 3 are both carbon, the carbonized carbon layer 3 is carbonized when the fibrous carbonized layer 4 is welded and entangled with the base ends of the individual carbon nanotubes of the carbon nanotube layer 3. Retained in layer 4.
  • the manufacturing apparatus 11 combines the substrate (holding the carbon nanotube group 30) K and the film sheet 40 and the delivery unit 12 that sends out the carbon sheet group 30 and the film sheet 40.
  • the carbonized sheet 14 to carbonize the film sheet 40 of the composite sheet 10 to make the composite sheet 10 the carbon nanotube sheet 1, and the carbon nanotube layer 3 of the carbon nanotube sheet 1 are held.
  • a substrate K is peeled from the carbon nanotube sheet 1 and a recovery unit 15 that recovers the carbon nanotube sheet 1 is provided.
  • the said composite part 13 and the carbonization part 14 perform the composite process 73 and the carbonization process 74 in the said manufacturing method, respectively.
  • the carbon nanotube group 30 (also the substrate K holding this) and the film sheet 40 are both belt-like and are sent batchwise or continuously from the sending unit 12 to the collecting unit 15 in the longitudinal direction. is there.
  • the carbon nanotube group 30 becomes the carbon nanotube layer 3 at the composite portion 13
  • the film sheet 40 becomes the fibrous carbonized layer 4 at the carbonized portion 14.
  • the said manufacturing apparatus 11 has many rolls mentioned later, and as for these rolls, all have the axial center arrange
  • the delivery unit 12 includes a first unwinding roll 21 and a second unwinding roll 22.
  • the first unwinding roll 21 is provided with a roll of a substrate (holding the carbon nanotube group 30) K so that the carbon nanotube group 30 can be sent out together with the substrate K batchwise or continuously.
  • the second unwinding roll 22 is provided with a roll of the film sheet 40 so that the film sheet 40 can be fed out batchwise or continuously.
  • the sending unit 12 has upper and lower guide rolls 24 in order to send the substrate K and the carbon nanotube group 30 and the film sheet 40 held on the substrate K to the composite unit 13 from a sent-out posture to a horizontal posture. .
  • the upper and lower guide rolls 24 are arranged at an interval that brings the substrate (holding the carbon nanotube group 30) K and the film sheet 40 asymptotically close to each other and does not contact the composite portion 13.
  • the roll-shaped substrate (holding the carbon nanotube group 30) K installed on the first unwinding roll 21 is in a direction in which the carbon nanotube group 30 faces the film sheet 40 in the fed state, that is, the substrate K. Is in a direction in contact with the guide roll 24.
  • the composite unit 13 presses the substrate (holding the carbon nanotube group 30) K and the film sheet 40 to provide upper and lower press rolls 31 (31a, 31b) for combining the carbon nanotube group 30 and the film sheet 40.
  • the upper and lower press rolls 31 press the substrate K (holding the carbon nanotube group 30) K and the film sheet 40 between them and pass through them.
  • the press roll 31 (31b) on the film sheet 40 side is provided with a heating device 34 for heating the film sheet 40 to be passed and pressed.
  • the carbonization section 14 can be placed in an inert gas atmosphere and a heating furnace 41 that heats the composite sheet 10 through the interior, and supplies an inert gas (for example, nitrogen gas) to the heating furnace 41.
  • a pump 48 for discharging gas from the inside of the heating furnace 41.
  • the gas supply device 47 and the pump 48 are connected to the inside of the heating furnace 41 via a pipe 49 and a valve (not shown), respectively.
  • the heating furnace 41 includes an in-furnace electric heater 44 for raising the temperature of the inside to a predetermined temperature.
  • the film sheet 40 is contracted by being heated to become the fibrous carbonized layer 4. This shrinkage causes the produced carbon nanotube sheet 1 to bend.
  • the stiffening belt (an example of a stiffening member) 61 for passing the film sheet 40 (carbonized layer 4) inside the heating furnace 41 to maintain the planar shape is passed.
  • the stiffening belt 61 is tensioned to maintain its flatness, and is preferably made of metal in order to withstand this tension and heating.
  • a tension roll 65 on which the stiffening belt 61 is stretched on the downstream side of the heating furnace 41 and a driving roll 66 that drives the stiffening belt 61 are disposed. That is, the rolls 31b, 65, 66 on which the stiffening belt 61 is stretched are the press roll 31 (31b), the tension roll 65, and the drive roll 66 on the film sheet 40 side.
  • the collection unit 15 is disposed on the substrate K side and guides the substrate K in the direction of peeling the substrate K from the carbon nanotube sheet 1; the substrate collection roll 51 that collects the substrate K peeled from the carbon nanotube sheet 1; A product recovery table 52 for recovering the carbon nanotube sheet 1 as a product from which the substrate K has been peeled off is provided.
  • the manufacturing method of the carbon nanotube sheet 1 using this manufacturing apparatus 11 will be described in detail.
  • the carbon nanotube layer 3 is formed on the surface of the belt-like substrate K, and the carbon nanotube group 30 held on the substrate K is rolled together with the substrate K.
  • this roll-shaped substrate (holding the carbon nanotube group 30) K is set on the first unwinding roll 21, and a separately prepared roll-shaped film sheet 40 is set on the second unwinding roll 22.
  • the substrate K is unwound from the first unwinding roll 21, and the unwound substrate K is transferred between the one guide roll 24 and the upper and lower press rolls 31 to the inside of the heating furnace 41 and the peeling roll 55. Then, the substrate is collected by the substrate collecting roll 51.
  • the film sheet 40 is unwound from the second unwinding roll 22, and the unwound film sheet 40 is passed into the heating furnace 41 between the other guide roll 24 and the upper and lower press rolls 31.
  • the product is recovered by the product recovery table 52.
  • the film sheet 40 is arrange
  • the inside of the heating furnace 41 is put into a nitrogen gas atmosphere by discharging the gas from the inside of the heating furnace 41 with the pump 48. Further, the inside of the heating furnace 41 is heated to a predetermined temperature (for example, 400 ° C.) by the in-furnace electric heater 44.
  • the predetermined temperature is 400 to 700 ° C., preferably about 600 ° C.
  • the temperature raising time is 1 to 10 ° C./min, preferably 2 to 5 ° C./min.
  • the press roll 31b is heated to another predetermined temperature (for example, 130 ° C.) by the heating device 34 of the press roll 31 (31b) on the film sheet 40 side.
  • the substrate collection roll 51 and the drive roll 66 are rotated to batch-feed the substrate K and the film sheet 40 (carbonized layer 4 after the carbonization unit 14) from the delivery unit 12 to the collection unit 15.
  • the film sheet 40 is heated by the press roll 31 and pressed against the carbon nanotube group 30 (for example, 2 MPa). This pressing is generally 6 to 15 MPa, but may be 2 to 30 MPa.
  • the composite sheet 10 is heated in a nitrogen gas atmosphere inside the heating furnace 41, but the carbon nanotube layer 3 does not react, but the film sheet 40 is carbonized to form a fibrous carbonized layer 4. become.
  • the carbonized portion 14 stops the composite sheet 10 for a predetermined time (for example, 2 to 3 hours) and is heated at the predetermined temperature.
  • the film sheet 40 is contracted by being heated to become the fibrous carbonized layer 4, but is in contact with (restricted by) the stiffening belt 61, so that the carbon nanotube sheet 1 does not bend.
  • the planar shape is maintained.
  • the individual carbon nanotubes in the carbon nanotube layer 3 approach each other, so that the density of the carbon nanotube layer 3 is increased.
  • the substrate K is separated from the carbon nanotube sheet 1 by the separation roll 55, the substrate K is collected by the substrate collection roll 51, and the carbon nanotube sheet 1 is collected in a batch by the product collection stage 52. Is done.
  • the electrical resistance of the carbon nanotube sheet 1 thus recovered was 0.05 ⁇ .
  • the carbon nanotube sheet 1 having low conductivity improvement of the characteristics of the carbon nanotube
  • the film sheet 40 becomes the fibrous carbonized layer 4 and contracts until the area becomes about one-fourth.
  • the carbon nanotube layer 3 held by the fibrous carbonized layer 4 is reduced. This is because the density is increased by about 4 times.
  • the manufacturing method of the carbon nanotube sheet 1 according to the first embodiment even if the carbon nanotube sheet 1 has a large area such that it is recovered by a roll, the sheet shape does not collapse, The carbon nanotube layer 3 can be obtained.
  • the carbon nanotube layer 3 in the carbon nanotube sheet 1 is densified, the characteristics of the carbon nanotube can be improved. Furthermore, since the carbon nanotube sheet 1 does not bend, a planar carbon nanotube sheet 1 having a highly versatile shape can be obtained.
  • the manufacturing efficiency can be improved.
  • the carbon nanotube layer 3 is held on the surface (that is, one side) of the fibrous carbonized layer 4 (see FIG. 1), but the carbon nanotube sheet according to Example 2 1, the carbon nanotube layer 3 is held on the front and back surfaces (that is, both surfaces) of the fibrous carbonized layer 4 (see FIG. 6).
  • the manufacturing method according to the second embodiment will be described. The configuration different from the first embodiment will be described, and the same components as those of the first embodiment will be denoted by the same reference numerals and the description thereof will be omitted.
  • the film sheet 40 is sandwiched between the front and rear surfaces of the carbon nanotube group 30 as the pressing of the film sheet 40 against the carbon nanotube group 30 in the composite step 73 of the manufacturing method according to the first embodiment. It is what I did.
  • the delivery unit 12 in the manufacturing apparatus 11 also has a third unwinding roll 23.
  • the third unwinding roll 23 is provided with a roll of a substrate (holding the carbon nanotube group 30) K, and the carbon nanotube group 30 is continuously formed together with the substrate K. Can be sent out. Further, the third unwinding roll 23 is arranged so that the second unwinding roll 22 is positioned between the first unwinding roll 21.
  • the upper and lower guide rolls 24 of the delivery unit 12 are asymptotically brought close to the upper and lower substrates (respectively holding the carbon nanotube group 30) K and the film sheet 40 therebetween, and are not in contact with each other up to the composite unit 13. Is arranged in.
  • the upper and lower press rolls 31 of the composite unit 13 in the manufacturing apparatus 11 are pressed so as to be sandwiched between the carbon nanotube groups 30 from the front and back surfaces of the film sheet 40, respectively, and the upper and lower carbon nanotube groups 30 and the film sheet 40 between them. It is for combining.
  • both the upper and lower press rolls 31 (31a, 31b) are provided with a heating device 34. Yes.
  • a stiffening plate 64 (an example of a stiffening member) 64 is disposed inside the heating furnace 41 of the carbonization unit 14 in the manufacturing apparatus 11 instead of the stiffening belt 61.
  • the stiffening plate 64 is for holding the composite sheet 10 (carbon nanotube sheet 1) together with the upper and lower substrates K to keep its planar shape and prevent bending.
  • the collection unit 15 in the manufacturing apparatus 11 includes two peeling rolls 55, that is, upper and lower peeling rolls 55 (55a and 55b).
  • the upper peeling roll 55a is for peeling the substrate K positioned on the carbon nanotube sheet 1
  • the lower peeling roll 55b is for peeling the substrate K positioned under the carbon nanotube sheet 1.
  • the collection unit 15 includes two substrate collection rolls, that is, upper and lower substrate collection rolls 51 and 53.
  • One substrate collection roll 51 collects one substrate K peeled from the carbon nanotube sheet 1
  • the other substrate collection roll 53 collects the other substrate K peeled from the carbon nanotube sheet 1. Is.
  • the upper and lower substrate recovery rolls 51 and 53 are arranged so that the product recovery platform 52 is positioned between them.
  • a roll-shaped substrate (holding the carbon nanotube group 30) K is previously installed not only on the first unwinding roll 21 but also on the third unwinding roll 23.
  • the substrate K is also unwound from the third unwinding roll 23, and the unwound substrate K is transferred to the other guide roll 24, the other press roll 31b, the inside of the heating furnace 41, and the other peeling roll 55b. Then, it is taken up by the other substrate collection roll 53.
  • the film sheet 40 unwound from the second unwinding roll 22 is positioned between the upper and lower guide rolls 24 and between the upper and lower press rolls 31 so that it is positioned between the upper and lower carbon nanotube groups 30.
  • the product is delivered to the inside of the product 41 and collected by the product collection table 52.
  • the upper and lower substrates K are sandwiched between the stiffening plates 64 inside the heating furnace 41.
  • the upper and lower substrate collecting rolls 51 and 53 are rotated, and the upper and lower substrates K and the film sheet 40 (carbonized layer 4 after the carbonizing unit 14) are continuously sent from the sending unit 12 to the collecting unit 15.
  • the film sheet 40 is pressed by the press roll 31 so as to be sandwiched between the upper and lower carbon nanotube groups 30 from the front and back surfaces thereof.
  • the film sheet 40 is contracted by being heated to become the fibrous carbonized layer 4, but is sandwiched (regulated) by the stiffening plate 64, so that the carbon nanotubes are flat without being bent. The shape is retained.
  • the individual carbon nanotubes in the carbon nanotube layer 3 approach each other, so that the density of the carbon nanotube layer 3 is increased.
  • the effects of the first embodiment are exhibited and the continuously manufactured carbon nanotube layer 3 is a surface of the fibrous carbonized layer 4. Since it is hold
  • the carbon nanotube layer 3 of the carbon nanotube sheet 1 manufactured by this manufacturing method includes an aspect (see FIG. 8) including a sparse layer 3s close to the carbonized layer 4 and a dense layer 3d far from the carbonized layer 4.
  • an embodiment see FIG. 9) that includes a dense layer 3 d on the side close to the layer 4 and a sparse layer 3 s on the side far from the carbonized layer 4.
  • the manufacturing apparatus 11 according to the third embodiment is different from the manufacturing apparatus 11 according to the first embodiment only in what is installed on the first unwinding roll 21. Specifically, two vertically aligned carbon nanotube groups are pressed together to form one sheet, and the substrate K holding this 30 is formed into a roll shape in the first winding according to the third embodiment. Installed on the take-out roll 21. Note that the length and / or density of the carbon nanotubes constituting the two vertically aligned carbon nanotube groups are different from each other. These lengths and / or densities are determined based on the porosity and thickness of the carbon nanotube layer 3 to be obtained. Other configurations and manufacturing methods of the manufacturing apparatus 11 are the same as those according to the first embodiment.
  • the effects of the first embodiment can be achieved and the porosity and thickness of the carbon nanotube layer 3 to be obtained can be adjusted.
  • the carbon nanotube layer 3 of the carbon nanotube sheet 1 manufactured by this manufacturing method includes an aspect (see FIG. 10) including a sparse layer 3s on the side close to the carbonized layer 4 and a dense layer 3d on the side far from the carbonized layer 4.
  • an embodiment see FIG. 11 that includes a dense layer 3 d on the side close to the layer 4 and a sparse layer 3 s on the side far from the carbonized layer 4.
  • the manufacturing apparatus 11 according to the fourth embodiment is different from the manufacturing apparatus 11 according to the second embodiment only in what is installed on the first unwinding roll 21 and the third unwinding roll 23. Specifically, two vertically aligned carbon nanotube groups are pressed together to form one sheet, and the substrate K holding this 30 in a roll shape is the first winding according to the fourth embodiment. Installed on the unwinding roll 21 and the third unwinding roll 23. Note that the length and / or density of the carbon nanotubes constituting the two vertically aligned carbon nanotube groups are different from each other. These lengths and / or densities are determined based on the porosity and thickness of the carbon nanotube layer 3 to be obtained. The other configuration and manufacturing method of the manufacturing apparatus 11 are the same as those according to the second embodiment.
  • the effects of the second embodiment can be obtained and the porosity and thickness of the carbon nanotube layer 3 to be obtained can be adjusted.
  • nitrogen gas has been described as an example of an inert gas, but the present invention is not limited to this, and may be a gas of a rare gas element such as helium, neon, or argon.
  • the carbonization process is performed after the composite process, but it is needless to say that the composite process and the carbonization process may be performed simultaneously.
  • thermocarbonized sheet 40 made of thermosetting resin or the non-woven fabric sheet derived from wood has been described as an example of the thermocarbonized sheet.
  • the present invention is not limited to this, and is heated. As long as it is carbonized and becomes fibrous.
  • the substrate K and the film sheet 40 are sent batchwise, but may be sent continuously. Thereby, manufacturing efficiency can be further improved.
  • the carbon nanotubes of the carbon nanotube layer 3 were not described in detail, but they were either single wall nanotubes or multiwall nanotubes (including double wall nanotubes). May be.
  • the pressing of the film sheet 40 against the carbon nanotube group 30 in the composite process has not been described in detail.
  • the part may fall and the intermediate part may be in an entangled state (crush until the thickness of the carbon nanotube group 30 is about 1 ⁇ 2 or less).
  • the carbon nanotube sheet 1 shown in FIG. 1B that is, the carbon nanotube sheet 1 in which the carbon nanotube layer 3 is entangled is obtained. Therefore, by using such a manufacturing method, the effects of the above-described Examples 1 to 4 can be obtained, and the wettability and thermal conductivity of the obtained carbon nanotube sheet 1 can be improved, and the sheet shape can be maintained. Can be made stronger.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
PCT/JP2014/064358 2013-06-05 2014-05-30 カーボンナノチューブシートおよびカーボンナノチューブシートの製造方法 WO2014196459A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP14808111.0A EP3006398A4 (de) 2013-06-05 2014-05-30 Kohlenstoffnanoröhrenfolie und herstellungsverfahren für kohlenstoffnanoröhrenfolie
KR1020157030747A KR102293908B1 (ko) 2013-06-05 2014-05-30 카본나노튜브시트 및 카본나노튜브시트의 제조방법
US14/895,061 US9902618B2 (en) 2013-06-05 2014-05-30 Carbon nanotube sheet and production method for carbon nanotube sheet
CN201480022076.2A CN105164049B (zh) 2013-06-05 2014-05-30 碳纳米管片材及碳纳米管片材的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-118393 2013-06-05
JP2013118393A JP2014234339A (ja) 2013-06-05 2013-06-05 カーボンナノチューブシートおよびカーボンナノチューブシートの製造方法

Publications (1)

Publication Number Publication Date
WO2014196459A1 true WO2014196459A1 (ja) 2014-12-11

Family

ID=52008105

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/064358 WO2014196459A1 (ja) 2013-06-05 2014-05-30 カーボンナノチューブシートおよびカーボンナノチューブシートの製造方法

Country Status (6)

Country Link
US (1) US9902618B2 (de)
EP (1) EP3006398A4 (de)
JP (1) JP2014234339A (de)
KR (1) KR102293908B1 (de)
CN (1) CN105164049B (de)
WO (1) WO2014196459A1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6482966B2 (ja) * 2015-06-25 2019-03-13 日立造船株式会社 カーボンナノチューブウェブの製造方法、カーボンナノチューブ集合体の製造方法およびカーボンナノチューブウェブの製造装置
KR102570247B1 (ko) 2015-12-28 2023-08-23 히다치 조센 가부시키가이샤 카본나노튜브 복합재 및 카본나노튜브 복합재의 제조방법
TWI725099B (zh) * 2015-12-28 2021-04-21 日商日立造船股份有限公司 奈米碳管接合片的製造方法
JP6917725B2 (ja) * 2017-02-13 2021-08-11 日立造船株式会社 カーボンナノチューブ複合材の製造方法、カーボンナノチューブ複合材および異方性カーボンナノチューブ複合材
JP7054734B2 (ja) 2017-12-07 2022-04-14 リンテック・オヴ・アメリカ，インコーポレイテッド 基材間のナノファイバーフォレストの転写
US11135827B2 (en) * 2018-10-11 2021-10-05 Lintec Of America, Inc. Patterning a nanofiber forest
US11479438B2 (en) * 2019-05-16 2022-10-25 Lintec Of America, Inc. Nanofiber structure applicator
WO2023085215A1 (ja) * 2021-11-12 2023-05-19 日本ゼオン株式会社 太陽電池用電極、太陽電池、および太陽電池モジュール

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006247758A (ja) * 2005-03-08 2006-09-21 Nagoya Institute Of Technology カーボンナノ構造材の製造方法、フィールドエミッションディスプレイおよび走査型プローブ顕微鏡
JP2007035811A (ja) * 2005-07-26 2007-02-08 Hitachi Zosen Corp カーボンナノチューブを用いた電極およびその製造方法
JP2007515364A (ja) * 2003-10-16 2007-06-14 ザ ユニバーシティ オブ アクロン カーボンナノファイバ基板上のカーボンナノチューブ
JP2009149517A (ja) 2009-03-30 2009-07-09 Univ Of Tokyo カーボンナノチューブ自立膜及びその製造方法、並びにカーボンナノチューブ膜を有する構成体及びその製造方法
JP2010512298A (ja) * 2006-12-14 2010-04-22 ユニバーシティー オブ ウロンゴング ナノチューブとカーボン層とのナノ構造複合体
JP2012166988A (ja) * 2011-02-15 2012-09-06 Taiyo Nippon Sanso Corp Ｃｎｔ製造用の四層型触媒基体、基板炭化層付きｃｎｔ、炭化層付きｃｎｔ、ｃｎｔ製法、ｃｎｔ回収方法及びｃｎｔ連続製造装置
JP2013510789A (ja) * 2009-11-13 2013-03-28 コミッサリア ア レネルジ アトミク エ オ エネルジ アルテルナティヴ カーボンナノチューブを基板上に合成する方法
WO2014087735A1 (ja) * 2012-12-07 2014-06-12 日立造船株式会社 カーボンナノ接合導電材料基板の製造方法、およびカーボンナノ接合導電材料基板の製造装置

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6024350A (en) * 1997-01-14 2000-02-15 Black & Decker Inc. Clamp for a power tool
US20100173228A1 (en) 2006-12-14 2010-07-08 University Of Wollongong Nanotube and Carbon Layer Nanostructured Composites
CN101462391B (zh) * 2007-12-21 2013-04-24 清华大学 碳纳米管复合材料的制备方法
CN101480858B (zh) 2008-01-11 2014-12-10 清华大学 碳纳米管复合材料及其制备方法
CN101456277B (zh) * 2007-12-14 2012-10-10 清华大学 碳纳米管复合材料的制备方法
CN103079805B (zh) 2009-12-14 2015-02-11 应用纳米结构方案公司 含有碳纳米管并入的纤维材料的防火复合材料和制品
CN101798076B (zh) * 2010-04-02 2012-02-29 上海交通大学 基于玻璃碳和碳纳米管的复合薄板的制备方法
CN101880036B (zh) * 2010-06-29 2013-02-13 清华大学 碳纳米管复合结构
CN103058167B (zh) * 2012-12-05 2015-05-20 天津大学 碳纳米管和碳的复合材料及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007515364A (ja) * 2003-10-16 2007-06-14 ザ ユニバーシティ オブ アクロン カーボンナノファイバ基板上のカーボンナノチューブ
JP2006247758A (ja) * 2005-03-08 2006-09-21 Nagoya Institute Of Technology カーボンナノ構造材の製造方法、フィールドエミッションディスプレイおよび走査型プローブ顕微鏡
JP2007035811A (ja) * 2005-07-26 2007-02-08 Hitachi Zosen Corp カーボンナノチューブを用いた電極およびその製造方法
JP2010512298A (ja) * 2006-12-14 2010-04-22 ユニバーシティー オブ ウロンゴング ナノチューブとカーボン層とのナノ構造複合体
JP2009149517A (ja) 2009-03-30 2009-07-09 Univ Of Tokyo カーボンナノチューブ自立膜及びその製造方法、並びにカーボンナノチューブ膜を有する構成体及びその製造方法
JP2013510789A (ja) * 2009-11-13 2013-03-28 コミッサリア ア レネルジ アトミク エ オ エネルジ アルテルナティヴ カーボンナノチューブを基板上に合成する方法
JP2012166988A (ja) * 2011-02-15 2012-09-06 Taiyo Nippon Sanso Corp Ｃｎｔ製造用の四層型触媒基体、基板炭化層付きｃｎｔ、炭化層付きｃｎｔ、ｃｎｔ製法、ｃｎｔ回収方法及びｃｎｔ連続製造装置
WO2014087735A1 (ja) * 2012-12-07 2014-06-12 日立造船株式会社 カーボンナノ接合導電材料基板の製造方法、およびカーボンナノ接合導電材料基板の製造装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3006398A4 *

Also Published As

Publication number Publication date
EP3006398A1 (de) 2016-04-13
US20160145105A1 (en) 2016-05-26
KR102293908B1 (ko) 2021-08-24
EP3006398A4 (de) 2017-01-18
KR20160014588A (ko) 2016-02-11
JP2014234339A (ja) 2014-12-15
CN105164049B (zh) 2018-04-20
US9902618B2 (en) 2018-02-27
CN105164049A (zh) 2015-12-16

Similar Documents

Publication Publication Date Title
WO2014196459A1 (ja) カーボンナノチューブシートおよびカーボンナノチューブシートの製造方法
Zhang et al. Ultrathick and highly thermally conductive graphene films by self-fusion
CN102652192B (zh) 柔性碳纤维非织造布
US8597526B2 (en) Method for making graphene/carbon nanotube composite structure
US8389119B2 (en) Composite thermal interface material including aligned nanofiber with low melting temperature binder
US8920661B2 (en) Method for making graphene/carbon nanotube composite structure
JPWO2006051782A1 (ja) 金属基炭素繊維複合材料およびその製造方法
JP2018535131A (ja) 形状適応性複数層複合材
WO2011118757A1 (ja) Ｃ／ｃコンポジット材及びその製造方法
WO2016029715A1 (zh) 一种石墨烯复合材料及其制备方法
TW201247424A (en) Method for manufacturing a graphene/ carbon nanotube composite
JP6703427B2 (ja) 複合織物の製造方法
CN104944409A (zh) 碳纳米管阵列的转移方法及碳纳米管结构的制备方法
JP2021511276A (ja) ナノファイバーシート組立体
WO2019087846A1 (ja) 表面層付き成形断熱材及びその製造方法
TW200936821A (en) Crucible holding member and method for producing the same
JP6456449B2 (ja) カーボンナノチューブシートの製造方法
TW201041256A (en) Method for producing flexible metal contacts
JP2005041193A (ja) ＳｉＣ質構造体
JP5463566B2 (ja) 成形体およびその製造方法
JP7235651B2 (ja) カーボンナノチューブ成形体の製造方法およびカーボンナノチューブ成形体の製造装置
WO2017122627A1 (ja) 熱電変換材料及び熱電変換デバイス
TWI440735B (zh) 奈米碳管膜之製備方法
JP2013121786A (ja) アブレータ
JP7105234B2 (ja) ナノファイバー熱界面材料

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201480022076.2

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14808111

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20157030747

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2014808111

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14895061

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE